JPH0395152A - Novel phenol derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (Y is group of formula II, etc.; R1, R2 and R3 are H, <=10C alkylphenyl or Y; R4 and R6 are H, Y, CH2OH, etc,; R5 and R7 are H, OH, <=10C alkyl). EXAMPLE:4-Hydroxy benzyl urea. USE:Useful as a molding material, laminate material, adhesive raw material, etc. The compound provides an inexpensive, highly curable and highly heat- resistant resin which is the initial condensate of a thermosetting resin. PREPARATION:A phenolic compound of formula III is reacted with an urea compound of formula IV in the presence of an acidic catalyst (e.g. sulfuric acid) in an aqueous solvent at a pH of 1-6 at 50-130 deg.C provide the compound of formula I. The co-condensate of the urea compound and the phenolic compound with formaldehyde is readily prepared without causing the condensation of two molecules of the urea compound with formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel phenol derivative and a method for producing the same. More specifically, the present invention relates to a novel phenol derivative, a formaldehyde cocondensate of phenols and urea that does not involve formaldehyde condensation between ureas, and a method for effectively producing the same.

The novel phenol derivatives, particularly the cocondensates, of the present invention are industrially useful as molding materials, laminates, adhesive raw materials, and the like.

(Prior Art) Thermosetting resins have been widely used as molding materials, laminates, adhesives, etc., and are important as industrial materials.

Among them, phenol resin, which is a condensation of phenol and formaldehyde, and urea resin, which is a condensation of urea and formaldehyde, are representative and generally widely used.

(Problem to be solved by the invention) Although urea resin is inexpensive and cures quickly, it has insufficient heat resistance and hydrolysis resistance.For example, in the case of adhesives, it is difficult to use it outdoors. It has poor quality and cannot be used.

On the other hand, phenolic resins have good heat resistance, durability, and hydrolysis resistance, but have the disadvantage of slow curing.

Therefore, there has been a strong desire for a co-condensation resin that improves these drawbacks and combines the advantages of both.

However, the formaldehyde condensation reaction between ureas is faster than the formaldehyde condensation reaction between phenols and urea, or the formaldehyde condensation reaction between phenols. The production of formaldehyde cocondensation resin with urea and urea was difficult.

The formaldehyde condensation of urea is generally inferior in heat resistance and hydrolysis resistance compared to the formaldehyde condensation of phenols and urea, or the formaldehyde condensation of phenols. Formaldehyde cocondensation resins of phenols and urea have durability close to that of urea resins, and are not sufficiently improved cocondensation resins.

Many proposals have been made to improve the formaldehyde cocondensate of phenol and urea.

For example, in JP-A-50-76145, a melamine urea formaldehyde initial condensate and an alkali phenol formaldehyde initial condensate are mixed and then co-condensed, so formaldehyde condensation of melamine or urea naturally exists.

Further, a formaldehyde co-condensate of phenol and urea, which is obtained by simultaneously reacting phenols, ureas, and aldehydes, is disclosed in Japanese Patent Publication No. 51-20540. exists.

As described above, in the prior art, an ideal formaldehyde co-condensate of phenols and ureas has not yet been developed.

(Means for Solving the Problems) As a result of intensive studies regarding formaldehyde co-condensation of phenols and ureas, the present inventors found that methylolated phenols can be co-condensed under acidic conditions and in the substantial absence of aldehydes. It was discovered that a formaldehyde co-condensate of phenols and urea, which has excellent curability and durability, can be easily obtained by reacting urea with urea, without formaldehyde condensation between ureas. It was completed.

That is, the present invention provides general formula (I) (In the formula, Y is selected from the groups represented by the following formula.

In the formula, R+. R2. R3 is a hydrogen atom, an alkyl group having 10 or less carbon atoms, a phenyl group, or -Y, which may be the same or different, and R-. Ra and R8 are hydrogen atoms, which may be the same or different, -Y, -CH2 0}
1 or U R, . R2, R. are the same as above, R,, R7 are H
Or it represents an alkyl group having 10 or less carbon atoms. ) and a method for producing the same.

The present invention will be explained in detail below.

The novel phenol derivatives of the present invention are represented by the general formula (I), such as 4-hydroxybenzyl urea, 2-hydroxybenzyl urea, 5-methylol-4-hydroxybenzyl urea, 3-methylol-2-hydroxybenzyl urea, urea, 5-methylol-2-hydroxybenzylurea, 3,5-dimethylol-2-hydroxybenzylurea, 3-methylol-4-hydroxybenzylurea, 3,5-dimethylol-4-hydroxybenzylurea, 2- Isobroby-5-hydroxybenzyl urea, 2-hydroxy-6-year-old cutylpenzyl urea, N-ethyl-N'-(4-hydroxybenzyl) urea, N,N-diethyl-N'-(4-hydroxybenzyl) urea, N,N'-bis(4-hydroxybenzyl)urea, tris(4-hydroxybenzyl)urea, N,N-bis(4-hydroxybenzyl)urea, tetrakis(4-hydroxybenzyl)urea,
2,4-dihydroxybenzyl urea, 2,6-dihydroxybenzyl urea, 2-hydroxy-4-methylol-penzyl urea, N-ethyl-N'-(2-hydroxybenzyl) urea, N,N-diethyl-N ′-(2
-hydroxybenzyl) urea, N,N'-bis(2
-hydroxybenzyl) urea, tris(2-hydroxybenzyl) urea, N,N-bis(2-hydroxybenzyl) urea, and the like.

Further, the production of the cocondensate with the novel phenol derivative represented by the general formula (1) of the present invention involves the production of a phenol compound represented by the following general formula (II-a) or (n-b) in an acidic aqueous solvent. The reaction is carried out by reacting the ureas and ureas represented by the following general formula (III).

or (in the formula, R4, Ra.Ra is a hydrogen atom or -CH.OH
,R,,R. represents a hydrogen atom, OH, or an alkyl group having 10 or less carbon atoms. ) R - R 2 H - N - C - N - R , (
II) 110 (In the formula, R..R2 and R3 represent the same groups as in the general formula (I) of the previous formula.) -M formula (II-a) or (n-b) used in the present invention The phenolic compound represented by
A phenolic substance having one or more methylol groups, such as 0-methylolphenol, p-methylolphenol, 2,4.6-trimethylolphenol,
2.4-dimethylolphenol, 2.6-dimethylolphenol, 2-methylolresorcinol, 4-methylolresorcinol, 2-methylol-3-ethylphenol, 2-methylol-3-isobrobylphenol, 2-methylol-5 -octylphenol, 3-
Examples include at least one selected from hexyl-4-methylolphenol, 3-isopropyl-4-methylolphenol, 3-octyl-4-methylolphenol, etc., condensates of these compounds, and alkali metal salts thereof. . These phenolic compounds can be easily obtained by reacting phenols with formaldehyde.

In the above reaction of the present invention, general formula (II-a)
When the phenolic compound represented by (n-b) has two or more methylol groups, a polymer or oligomer can be obtained.

In addition, in the present invention, as the compound represented by the general formula (II-a) or (n-b), an initial condensation product of phenol/formaldehyde obtained by reacting phenols with formaldehyde by a conventionally known method is also used. be done.

In this case, for example, 1.0 to 4.0 mol of formaldehyde, preferably 1.0 to 4.0 mol, per 1 mol of phenol.
．． 0 mol was reacted in the presence of an alkali.

Examples of the above-mentioned phenols include monovalent phenols such as phenol, cresol, xylenol, ethylphenol, p-tertiarybutylphenol, p-octylphenol, meditol, p-phenylphenol, resorcinol, catechol, hydroquinone,
Examples include one type or a mixture of two or more divalent phenols such as 4-methylresorcinol, 4-methyltecol, orcinol, 2-methylhydroquinone, β-orcinol, m-xylolcinol, and p-xylohydroquinone. It will be done.

The ureas represented by the general formula (In) used in the present invention include urea, N-ethylurea, N,N'-dimethylurea, and N,N-jethylurea alone or in mixtures.

The reaction between the phenolic compound represented by the general formula (II-a) or (II-b) and the urea represented by the general formula (III) can be carried out under acidic conditions in the substantial absence of aldehydes. This is an important point of the present invention.

The substantial absence of aldehydes preferably means that unreacted aldehydes present in the reaction solution are reduced to 1% or less.

When a substantial content of aldehydes is present, the general formula (rI
The urea represented by I) reacts with aldehyde, producing a methylolated product of urea, and further formaldehyde condensation of urea occurs, which is undesirable.

The ratio of the phenolic compound represented by the general formula (rl-a) or (II-b) and the urea represented by the general formula (III) is determined as appropriate within a range in which unreacted urea does not remain. The equivalent ratio of methylol groups to amine groups is preferably 0.3 to 5.0, more preferably 0.
It is in the range of 4 to 2.0.

If the equivalent ratio of methylol groups is less than 0.3, unreacted urea remains, which is not preferable. Moreover, if the equivalent ratio of methylol groups is 5.0 or more, the curability deteriorates, which is not preferable.

Note that depending on the use of the novel phenol derivative represented by general formula (I) in the present invention, the compound of general formula (I) may contain by-products during production as impurities. good.

Further, it may be a mixed composition in which two or more of these novel phenol derivatives are mixed together, or a condensation composition in which these novel phenol derivatives or a mixture thereof are further condensed.

In addition, in the reaction between a phenolic compound having two or more methylol groups and ureas, the molar ratio of the phenolic compound to 1 mole of the urea may be set to O, 90 to 1.1, for example.
By setting it to 0, an alternating formaldehyde cocondensate of phenol and urea can be obtained, and even better physical properties can be obtained.

When reacting the initial condensate of phenol/formaldehyde with urea, the equivalent ratio of the methylol groups of the initial condensate of phenol/formaldehyde to the amino groups of urea is adjusted to 0.3 to 5.0.

The reaction is carried out under acidic conditions, and the pH of the reaction solution is 1.0 to 6.0.
is appropriate, preferably 2.0 to 5.0.

If the pH of the reaction mixture is less than 1.0, the reaction will be too fast and it will be difficult to control the reaction, and if it is more than 6.0, the reaction time will be too long, which is undesirable.

Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. as acidic catalysts,
Organic acids such as acetic acid, formic acid, phthalic acid, maleic acid, and oxalic acid, and their salts that can make the reaction solution acidic can be used.

The acidic catalyst may be added in advance by dissolving it in the aqueous solvent, or after the phenols and urea are dissolved in the aqueous solvent.

The reaction temperature is desirably 50 to 130'C; if it is below 50C, the reaction time becomes too long, which is undesirable.

If the reaction temperature exceeds 130°C, the reaction will be too rapid and difficult to control.

The above reaction is preferably carried out in an aqueous solvent, but a water-soluble solvent such as methanol, ethanol, acetone, isopropyl alcohol, dioxane, etc.
May contain.

The actual use of the phenol derivative and co-condensate of the present invention can be carried out in the same manner as with conventional urea resins, and can also be mixed with conventional urea-formaldehyde resins (UF), melamine-formaldehyde resins (MF), etc. It is also possible to use

When used in combination with these conventional resins, it may be premixed or mixed immediately before use.

Furthermore, fillers, extenders, hardeners, etc. can be added if necessary.

(Effects of the Invention) The phenol derivative of the present invention corresponds to an initial condensate of a new thermosetting resin, and can itself be used as an adhesive, but further curing of the phenol derivative would result in problems that could not be achieved using conventional techniques. , it is possible to obtain a resin that is inexpensive, hardens quickly, and has high heat resistance.

The resin of the present invention can be used as a substitute for conventional phenolic resins and urea resins in all fields of application, and has great industrial and economic advantages.

According to the method of the present invention, a novel phenol derivative, particularly a cocondensate, can be obtained by the reaction of urea and a phenol compound without causing formaldehyde condensation of the ureas.

(Examples) In order to explain the present invention more specifically, Examples are shown, but the present invention is not limited to these Examples at all. In addition, 0-methylolphenol in the examples,
and p-methylolphenol from Aldrich Ch.
chemical Company, Inc. I used a manufactured product.

Moreover, the reaction conditions of Examples 1 to 3 are as shown in Table 1.

Reference Example 1 2 4 Synthesis of 6-1-limethylolphenol 40 g of sodium hydroxide was dissolved in 139 g of distilled water, cooled, and 94 g of phenol was dissolved.
．． 201.1 g of 8% formalin was added and reacted at 20° C. for one week.

Next, the reaction solution was poured into a 400ml isobrobyl alcohol container.

The precipitate was filtered, washed, and dried under vacuum to obtain 80 g of 2,4.6=trimethylolphenol.

Example 1 20.6 g of p-methylolphenol was added to 100 Tfl
The mixture was placed in a reaction vessel with a capacity of 1 liter and equipped with a condenser, and 20 liters of hot water was added thereto to dissolve it.

Then, 5% sulfuric acid was added to adjust the pH to 5.0. Furthermore, after dissolving 10 g of urea, the pH was adjusted to 3.0 using 50% sulfuric acid.

After reacting at 85° C. for 180 minutes with stirring, the mixture was cooled to obtain the desired cocondensate.

The product of Example 1 was separated into peaks 1 to 3 shown in FIG. 1 by GPC.

Peaks 1 to 3 were analyzed individually, and the IR chart is shown in FIG. 2, and the +3C-NMR chart is shown in FIG. 3.

The IR absorption at 1 640-1 650 cm" is due to the amine group.

Beak 1 shown in Figure 1 is a crystalline substance, estimated to be 4-hydroxybenzyl urea, and has an NMR value of 44.2p.
The pm signal is attributed to methylene carbon, and NM
The 160.4 ppm signal of R is swept to the carbonyl carbon.

Also, based on self-condensation of p-methylolphenol, <4
There is no signal at 0.5 ppm.

Based on the condensation between ureas, 47. '7pp
m signal (-N}l-CH2-NH-) and NM
53.5 ppm signal of R [-NH-Cl{. -N
(CH2-)-] also does not exist.

Note that the underlined methylene bond indicates the attribution of the NMR signal (
The same applies hereafter).

Furthermore, the results of elemental analysis shown in Table 2 are also close to the theoretical values.

Peak 2 shown in Figure 1 is a crystalline substance, N-,N
It is presumed to be '-bis(4-hydroxybenzyl) urea, and the NMR signal at 44.3 ppm is assigned to methylene carbon, and the NMR signal at 159.7 ppm is assigned to carbonyl carbon.

Based on the condensation between urea, <47.7 ppm of NMR
signal (-NH-C}l2-NH-1 and NMR
A signal of 53.5 ppm [-NH-CH2-N(C
Hz-)-] also does not exist.

Furthermore, the results of elemental analysis shown in Table 2 are also close to the theoretical values.

The material of beak 3 shown in FIG. 1 is an amorphous material expressed by the following formula, ? The pm signal is assigned to the methylene carbon in No. 8, and the 49.2 ppm NMR signal is assigned to the methylene carbon in B.

Also, based on self-condensation of p-methylolphenol, <4
There is no signal at 0.5 ppm.

Based on the condensation between urea, <47.7 ppm of NMR
signal (-NH-CHa-NH-) and an NMR signal of 53.5 ppm (-NH- group 2-N(Cli
■1) -1 does not exist.

Furthermore, the results of elemental analysis shown in Table 2 are close to the theoretical values.

The NMR signal at 159.3 ppm was assigned to carbonyl carbon, and NMR 44.7 Example 2 In place of p-methylolphenol in Example 1, 0
A viscous, night-like cocondensate was obtained in exactly the same manner as in Example 1, except that acetic acid was used instead of sulfuric acid for methylolphenol.

The NMR spectrum of this product is as shown in Figure 4, and the NMR signal at 44.6 ppm is assigned to the methylene bond of 2-hydroxy-benzyl urea, and the NMR signal at 1
The signal at 61.3 ppm is assigned to the carbonyl group of 2-hydroxypendylurea.

Based on the condensation between urea, <47.7 ppm of NMR
signal (-NH-Cl{2-NH-) and NMR
A signal of 53.5 ppm [-NH-CH2-N(C
H2-)-] also does not exist. Therefore this one is 2-
Estimated to be a combination of hydroxybenzyl urea, NN'bis(2-hydroxybenzyl) urea, N,N bis(2-hydroxybenzyl urea, tris(2-hydroxybenzyl) urea, and tetrakis(2-hydroxybenzyl) urea) be done.

Example 3 In place of p-methylolphenol in Example 1, 2.
4. Using 6-trimethylolphenol, urea 20.
A viscous, deformable co-condensate was obtained in exactly the same manner as in Example 1, except that 15 g was used.

The NMR spectrum of this product is as shown in Figure 5. The NMR signal at 40.5 ppm is attributed to the methylene bond between the 1st position and urea, and the NMR signal at 44.3 ppm is attributed to the methylene bond between the p1 position and urea. Attributed to methylene bond, 49.
The 2 ppm signal is assigned to the N-N2 substituted methylene bond.

And based on the condensation between urea <47.7pp of NMR
m signal (-NH-CH2-NH-) and NMR
A signal of 53.5 ppm [-NH-CH. -N(C
H2-)-] also does not exist. Therefore, this one is 2,
4-dihydroxybenzyl urea, 2,6-dihydroxybenzyl urea, N,N' (2,4-dihydroxybenzyl) urea, N,N' (2,6-dihydroxybenzyl) urea, tris(2,4-dihydroxybenzyl) ) urea, tris(2,6-dihydroxybenzyl)
Yuria, tetrakis (2,4-dihydroxybenzyl)
Yuria, tetrakis (2,6-dihydroxybenzyl)
It is estimated to be urea, N,N (2,4-dihydroxybenzyl)urea, N,N (2,6-dihydroxypenzyl)urea, and condensates thereof.

In this case, GPC (Gel Permeation C
For chromato (Hlaphy), a sample was dissolved in dimethylformamide (DMF) and detected using an R-401 differential refractometer (manufactured by Waters). Column is Shode
x AD2002 (manufactured by Showa Denko) was used while being kept at 60°C. The flow rate of DMF is 3. OITIii/m
It was in. In addition, in "C-NMR, the sample is viridin-d5
- and dissolve it in FT8CIAN MR (Vari
(manufactured by An).

Example 4 Into a reaction flask equipped with a reflux condenser, thermometer, stirrer, and addition funnel, 200 g of phenol, 37% formalin, 5
17g of NaOH and 42.4g of NaOH were charged and dissolved while cooling, and then reacted at 50'C for 8 hours. At this time, free formaldehyde was 0.7%.

After cooling to 35°C, 125 g of 50% sulfuric acid was added dropwise from the dropping funnel. At this time, the pH was 3.5. Then, 127 g of urea was added and reacted at 85° C. for 60 minutes.

Next, it was neutralized with N a C O 3 and then cooled.

The product separated into two layers. That is, it was separated into an upper layer (aqueous layer) and a lower layer (resin M). The aqueous layer was removed to obtain a co-condensate. This product was a viscous liquid co-condensate similar to Example 4, and was a phenolurea co-condensate resin and its condensate.

13C-NMR of the resin composition is shown in FIG. There is almost no signal for condensation between ureas.

Example 5 Into a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 200 g of phenol and 37% formalin 5 were added.
1 7g, prepare 1L, 8g of Ca (OH)2,
After dissolving while cooling, the mixture was reacted at 50° C. for 8 hours. At this time, free formaldehyde was 1.0%. 3
After cooling to 5°C, 40 g of 50% sulfuric acid was added dropwise through a dropping funnel.

At this time, the pH was 4.0. Then, 127 g of urea was added, reacted at 85° C. for 60 minutes, neutralized with NaOH, and then cooled. The product separated into two layers. That is, it was separated into an upper layer (aqueous layer) and a lower layer (resin layer). The aqueous layer was removed to obtain a co-condensate.

Reference Example 2 Phenol In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 200 g of phenol and 37% formalin were added.
76g of NaOH and 25.5g of NaOH were charged and dissolved while cooling, and then reacted at 80°C for 3 hours. After cooling to 50°C, 38.3 g of urea and 17 g of formaldehyde were added.
2 g was added and reacted at 75° C. for 120 minutes, followed by cooling.

The resulting resin liquid was reddish-brown and transparent, had a viscosity of 50 cp, and had a nonvolatile content of 55%. The NMR results are shown in FIG. There is almost no signal due to co-condensation.

Reference example 3 Phenonore! In a reaction flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 200 g of phenol and 37% formalin were added.
30.0g. 31.8 g of NaC)H was charged, dissolved while cooling, reacted at 80° C. for 2 hours, and then cooled. The resulting resin liquid was reddish-brown and transparent, with a viscosity of 50 cp.
, the non-volatile content was 56%.

Reference Example 4 Cuan Meng Shii Bi Dio 4 Into a reaction flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 300 g of urea and 608 g of 37% formalin were added.
Add 1 g of 20% NaOH, heat to pH 7.0 with stirring, react at 85°C for 30 minutes, adjust the pH to 5.0 using 40% acetic acid solution, and react at 85°C for 1 hour. After that, 20% NaOH was added to adjust the pH to 8.0, and the mixture was cooled.

The resulting resin liquid was milky white, had a viscosity of 38 cp, and had a non-volatile content of 5.
It was 7.2%.

(Adhesion test) Examples 6 to 11, Comparative Examples 1 to 5 The cocondensates of Examples 1 to 5 were prepared using a 1.6 mm thick veneer of lauan (water content 7%) made by L. Using the resins obtained in Reference Examples 2 to 4, adhesives were prepared at the compounding ratios shown in Table 3, and 3-brie plywood was produced under the following bonding conditions.
Adhesive strength was measured based on ordinary plywood standards. The results are shown in Table 4.

a) Compounding conditions They were blended in the proportions shown in Table 3.

b) Adhesion conditions Application amount 28g/900crr? (core board) 20 minutes 10k g/c resistance, 12kg/crrr, 3 minutes or 2 minutes, 120°C In addition, the blending ratio of each resin indicates parts by weight.

Cold Pressure Heat Pressure Table 3 Table 4 Numbers on the left: Tensile strength Numbers on the right: Wood yield (%) Special strength: Strength after 72 hours of continuous boiling Hardening agent: Ammonium chloride

[Brief explanation of drawings]

Figure 1 shows the GPC graph of the product of Example 1, and Figures 2 and 3 show the infrared absorption spectrum of the same product and the "C"
-NMR charts are shown respectively. Figure 4 shows the NMR spectrum of the product of Example 2, Figure 5 shows the NMR spectrum of the product of Example 3, Figure 6 shows the NMR spectrum of the product of Example 4, and Figure 7 shows the NMR spectrum of the product of Example 4. The figure shows the NMR spectrum of the product of Reference Example 2.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Y is selected from the groups represented by the following formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.) There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, and R_3 are hydrogen atoms that may be the same or different from each other, and the number of carbon atoms is 10 or less is an alkyl group, phenyl group, or -Y, and R_4, R_5, and R_8 are hydrogen atoms, -Y, and -C, which may be the same or different from each other.
H_2OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_1, R_2, R_3 are the same as above, R_5,
R_7 represents H, OH, or an alkyl group having 10 or less carbon atoms. ) A phenol derivative represented by 2. The compound represented by general formula (I) has a molecular weight of 15
The novel phenol derivative according to claim 1, which has a molecular weight of 0 to 3,000. 3. In general formula (I), R_1, R_2, R_3 are hydrogen atoms, or -Y, Y is o- or p-hydroxybenzyl group, or 2-hydroxy-3-methylolbenzyl or 2
-Hydroxy-5-methylolbenzyl group, 2-hydroxy-3,5-dimethylolbenzyl group or 4-hydroxy-3,5-dimethylolbenzyl group Claim 1
The novel phenol derivatives described. 4. R_1, R_2, R_3 in general formula (I) are hydrogen atoms, or -Y, Y is o- or p-hydroxybenzyl group, 2 (or 4)-hydroxy-3-methylolbenzyl, or 2 (or 4) The phenol derivative according to claim 1 or 2, which is a -hydroxy-5-methylolbenzyl group, a 2-hydroxy-3,5-dimethylol-benzyl group, or a 4-hydroxy-3,5-dimethylolbenzyl group, or contains the same. Composition. 5. Characterized by reacting a phenol compound represented by the following general formula (II-a) or (II-b) with a urea represented by the following general formula (III) in an acidic aqueous solvent. A method for producing a phenol derivative represented by the general formula (I) according to claim 1. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-a) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-b) (In the formula, R_4, R_5, R_8 are hydrogen atoms or -CH
_2OH, R_5, and R_7 represent a hydrogen atom, OH, or an alkyl group having 10 or less carbon atoms. )▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (III) (In the formula, R_1, R_2, R_3 are the general formula ( I
) indicates the same group. ) 6. The phenol derivative according to claim 5, wherein the phenol compound of general formula (II-a) or (II-b) is an initial condensate of phenol/formaldehyde obtained by reacting phenol and formaldehyde in the presence of an alkali. manufacturing method. 7. The method for producing a phenol derivative according to claim 6, wherein the phenol is one or a mixture of two or more of monovalent phenols or divalent phenols. 8. The phenolic compound of general formula (II) is o- and/
or p-methylolphenol, 2,4- and/or 2
, 6-dimethylol and/or 2,4,6-trimethylolphenol. 9. Claim 5, wherein the acidic aqueous solvent has a pH of 1.0 to 6.0.
A method for producing the described phenol derivative. 10. The phenol derivative according to claim 5, wherein the acidic aqueous solvent uses a mineral acid, an organic acid, or a salt thereof capable of making the reaction solution acidic. 11. A co-condensation composition containing one or more compounds represented by the general formula (I) according to claim 1. 12. An adhesive composition containing the phenol derivative according to claim 1.